CN105925340A - Process for synthetic lubricant production - Google Patents

Process for synthetic lubricant production Download PDF

Info

Publication number
CN105925340A
CN105925340A CN 201610267118 CN201610267118A CN105925340A CN 105925340 A CN105925340 A CN 105925340A CN 201610267118 CN201610267118 CN 201610267118 CN 201610267118 A CN201610267118 A CN 201610267118A CN 105925340 A CN105925340 A CN 105925340A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
feed
molecular weight
oligomerization
method
control
Prior art date
Application number
CN 201610267118
Other languages
Chinese (zh)
Inventor
A·O·帕蒂尔
N·扬
M·M·吴
Original Assignee
埃克森美孚化学专利公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/14Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20Acids of halogen; Salts thereof Complexes thereof with organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/14Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20Acids of halogen; Salts thereof Complexes thereof with organic compounds
    • C07C2/22Metal halides; Complexes thereof with organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/26Catalytic processes with hydrides or organic compounds
    • C07C2/32Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34Metal-hydrocarbon complexes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/08Halides
    • C07C2527/12Fluorides
    • C07C2527/1213Boron fluoride
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/125Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126Aluminium chloride
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22Organic complexes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14Monomers containing five or more carbon atoms
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1088Olefins
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material

Abstract

The invention relates to a process for synthetic lubricant production. The process for the preparation of oligomeric poly alpha-olefins includes oligomerizing low molecular weight PAO oligomer in the presence of a Lewis acid catalyst such as promoted aluminum trichloride or boron trifluoride under oligomerization conditions. The low molecular weight PAO oligomers used as a feed or feed component of the present process are the light olefinic by-product fractions including the dimers and light fractions from the metallocene-catalyzed PAO oligomerization process which are characterized by a molecular weight of 150 to 600 and a terminal olefin (vinylidene) content of at least 25%.

Description

合成润滑剂制备方法发明领域 Preparation of synthetic lubricants INVENTION Field

[0001] 本申请是中国专利申请200980109216.9的分案申请。 [0001] This application is a Chinese patent application is a divisional application 200,980,109,216.9. 本公开内容设及用作合成润滑剂基本原料的聚-a-締控(PAO)的改进生产方法。 The present disclosure is provided and associated control -a- poly (PAO) used as an improved method for producing the synthetic lubricant base stocks.

[0002] 发明背景 [0002] Background of the Invention

[0003] PAO已被认为是一类特别适合作为高性能合成润滑剂基本原料的材料超过30年之久。 [0003] PAO has been found to be particularly suitable as a class of high-performance synthetic lubricant base raw materials for more than 30 years. 它们具有良好的低溫流动性、较高的热和氧化稳定性、高溫下的低蒸发损失、高粘度指数、良好摩擦行为、良好水解稳定性、W及良好抗腐蚀性。 They have good low temperature fluidity, high thermal and oxidative stability, low evaporation losses at high temperatures, high viscosity index, good friction behavior, good hydrolytic stability, W, and good corrosion resistance. PAO是无毒的,且与矿物油、其它合成控液体、流体和醋混溶。 PAO is non-toxic, and with mineral oil, other synthetic control liquid, immiscible fluid and vinegar. 由此,PAO适合用于发动机油、压缩机油、液压油、齿轮油、油脂和功能流体。 Thus, PAO suitable for use in engine oils, compressor oils, hydraulic oils, gear oils, functional fluids and greases. 术语PAO已宽泛地且通常用作命名运些润滑剂基本原料,尽管在用作基本原料之前将初始締控低聚物氨化W除去残留不饱和度且改进润滑油产物的热和氧化稳定性。 The term & PAO is used broadly and generally designated transport some lubricant base stocks, although the base material before being used as the initial W associated control oligomer amide remove residual unsaturation lubricating oil and improved thermal and oxidative stability of the product . PAO 作为高品质润滑剂基本原料的用途包含在许多教科书的主题之中,例如Lubrication !^ndamental S ,JGWills, Marcel Dekker Inc.,(纽约,1980),W 及Synthetic Lubricants and High-Performance Functional Fluids ,第二片反,Rudnick和Shubkin, Marcel Dekker Inc.,(纽约,1999)。 PAO use as the basic raw material of high quality lubricant contained in the subject of many textbooks, for example Lubrication! ^ Ndamental S, JGWills, Marcel Dekker Inc., (New York, 1980), W and Synthetic Lubricants and High-Performance Functional Fluids, The second piece anti, Rudnick and Shubkin, Marcel Dekker Inc., (New York, 1999).

[0004] PAO可W通过使用弗瑞德-克来福特催化剂如S氯化侣或S氣化棚来制备,其中S 氣化棚是首选的催化剂。 [0004] PAO may be W by using Friedel - Crafts catalyst g prepared as chlorinated Lu S or S shed gasification, gasification shed where S is the preferred catalyst. 优选地将=氣化棚与质子促进剂,典型地醇如异丙醇或下醇、水、 或者酸、醋或酸结合,由此形成催化剂络合物,该催化剂络合物可W用于促进低聚成具有期望分子量高支化的低聚结构的产物,运对于润滑剂产品中低倾点和高粘度指数的组合而言是所需的。 Preferably the gasification = shed with a protic promoter, typically an alcohol or an alcohol such as isopropanol, water, or acid, acetic acid, or in combination, thereby forming the catalyst complex, the catalyst complex can be used for W promoting oligomerization to have a desired molecular weight highly branched oligomeric structure of the product, the product transport the lubricant composition of low pour point and high viscosity index terms is required. 通常使用的a締控是Cs~Ci4范围内的那些,优选1-辛締、1-癸締和1-十二碳締;已发现奇数碳原子数締控的使用是不利的。 A control associated generally used are those, 1-octene associative, 1-decene and 1-dodecene association Cs ~ Ci4 association within the range; odd number of carbon atoms have been found associated control use is disadvantageous. 运类締控可W典型地通过裂化或者通过乙締链增长工艺来形成。 W type associative operation can be controlled by cracking is typically formed by the association or B chain growth process. 低聚过程中通常使用的=氣化棚催化剂代表了用于制备聚a締控的工艺流程中显著的成本,因为其通常不能回收,而是相反地被水洗去活化。 Oligomerization process normally used in a gasification = shed catalyst represents a significant cost to a process for preparing polyethylene in association control, since they typically can not be recovered, but instead is washed deactivated. 用过的、去活化的催化剂通常在生产聚a締控的商业操作中通过深井灌注来处理,存在一些环境考虑因素的处理方法,虽然已提出了各种回收=氣化棚的方法。 Spent, deactivated catalyst is typically treated by perfusion of production of a poly A commercial operations associated controlled deep, some processing methods of environmental considerations, although proposed various methods of recovery = gasification shed.

[0005] 目前使用弗瑞德-克来福特催化剂的低粘度PAO工艺中,将二聚体或轻质馈分循环回线性a-締控进料中W制备更多润滑油基本原料。 [0005] Currently used Friedel - Crafts catalyst g of low viscosity PAO process, the split-cycle dimer or light fed back to control the feed of linear association a- W more lube base stock was prepared. 主要包含C姐16~C30H60低聚物(平均C20也0)的运些二聚体或轻质馈分,显示280或更低的较低平均分子量,且并非非常期望地作为该工艺的进料,由于伴随低聚过程的异构化,尽管在制备其为具有高粘度指数和低倾点的优异润滑剂的支链更高低聚物方面而言是有价值的,也形成由本身是高支化、高取代的产品(分子中间具有不饱和双键)的更低低聚物组成的二聚体或轻质馈分;它们通常可W特征在于在所述分子量范围内具有大量短链支化和高取代双键的低聚物(=-和四-取代締控)。 Mainly comprising a dimer or more light transport component C fed sister 16 ~ C30H60 oligomers (average C20 also 0), the display 280 or less, the lower the average molecular weight, and not very desirable as feed to the process Since accompanied by isomerization of the oligomerization process, although in terms of its higher oligomers prepared aspect branched excellent lubricant having a high viscosity index and a low pour point is valuable, is itself also formed from a highly branched and high-substituted products (having an unsaturated double bond among molecules) is more low-low oligomer dimer or light composed of feed points; W are usually characterized by having large numbers of short chain branching in the molecular weight range and highly substituted double bonds oligomer (= - and tetra - substituted association control). 由于空间上受阻,运些轻质副产物中的双键不易接近且由此不易受到进一步反应的影响。 Due to restricted space, light by-products transported more double bonds in the less accessible and therefore less affected by further reaction. 由此,运些二聚体或轻质馈分对于进一步低聚具有很小反应性。 Thus, these dimers or light transported for further oligomerization feed points has little reactivity. 另外,它们是更高支化的締控且源于运些支化分子的润滑油产物由于它们的结构而具有不太合乎需要的VI、挥发性和热/氧化稳定性。 In addition, they are more highly branched associated control and operation from those of the lube product molecules due to their branched structure having a VI of less desirable, volatility and thermal / oxidative stability. 由此在最终氨化步骤之前除去二聚体馈分(如US 3,149,178中所述) 成为常规操作。 Whereby prior to the final step of removing the amide dimer feed points (e.g., described in US 3,149,178) become a routine operation.

[0006] 对于高品质PAO、特别是低粘度/高VI/低倾点PAO的需求正变得紧迫,且一直在提出对于现有弗瑞德-克来福特工艺的替换形式。 [0006] PAO for high-quality, in particular the low viscosity / high VI / low pour point PAO becoming urgent demand, and has been proposed for conventional Friedel - Crafts g of alternative forms of the process. 已提出负载的、还原的铭催化剂和茂金属催化剂体系用于运些工艺。 It has made the load, reducing the Ming catalysts and metallocene catalyst systems for the transport of these processes. W02007/011973(Wu等)中描述了使用茂金属催化剂制备4~lOcS、 低粘度PAO基本原料的方法。 W02007 / 011973 (Wu et al.) Describes a method of preparing 4 ~ lOcS, low viscosity PAO base stocks metallocene catalyst. 运种技术由于基于茂金属的低粘度PAO具有优异润滑油性能而是有吸引力的。 Yun techniques has excellent lubricating oil properties based on low-viscosity PAO metallocene but rather attractive. 迄今为止运种方法的一个缺点在于,在制备4~IOcS PAO时,一些数量的二聚体或轻质馈分(小于C30) W副产物形式获得。 So far a disadvantage in that operation method, in the preparation of 4 ~ IOcS PAO, some amount of dimers or light feed fraction (less than C30) W obtained as a byproduct. 运些轻质締控不能够用作润滑剂基本原料, 因为它们挥发性太大,且由于它们通常是更高线性的W及具有高度的亚乙締基或乙締基含量而不可W循环回茂金属催化的工艺中。 These associative operation control can not be used as a light lubricant base stocks, because they are too volatile, and since they are generally more linear and has a height of W associative ethylene group or acetyl group content of the non-associative recycled to W metallocene-catalyzed process. 由此,茂金属低聚工艺中的轻质馈分如果它们不可W通过其它方法转化为润滑油产品,则代表了润滑油产率损失。 Accordingly, the metallocene oligomerization process light feed points if they are not in W into oil products by other methods, the yield represents the loss of the lubricant.

[0007] 共同待审的美国临时专利申请No.61/008,095(2007年12月18日提交),描述了由茂金属催化的低聚工艺中制得的低分子量O-締控低聚物制备高品质润滑油沸程产品的方法。 [0007] U.S. Provisional Patent co-pending Application No.61 / 008,095 (December 18, 2007 filed), describe the preparation made by the metallocene-catalyzed oligomerization process to obtain low molecular weight oligomer O- associated control the method of high-quality lubricating oil boiling range products. 茂金属低聚步骤中的轻质締控副产物的线性特征使得它们成为用作使用US No. 61/ 008095中所述离子液体催化剂的低聚工艺的进料的良好选择。 Wherein the linear light by-products associated control metallocene oligomerization step makes them a good choice to use as feed US No. oligomerization process of the ionic liquid catalyst in 61 / 008,095. 茂金属締控(主要为二聚体) 可W相对于路易斯酸催化工艺中获得的支化締控更容易地低聚或共低聚,且它们产生具有更少支链且由此更佳的润滑油性能的润滑油基本原料。 Metallocene association control (mainly dimers) may be W with respect to the Lewis acid catalyzed processes associated branching obtained more easily controlled oligomerization or co-oligomerization, and they produce fewer branches and thus better lube base stock lubricating properties.

[000引发明概述 [000 triggered Ming Overview

[0009] 来自茂金属低聚工艺的非润滑油沸程轻质締属馈分可W使用路易斯酸催化剂转化为高品质润滑油基本原料。 [0009] non-lube boiling range light from the metallocene oligomerization process genus associated feed points W using a Lewis acid catalyst may be converted into high quality lubricating oil base stocks. 采用此方式,可W显著提高来自茂金属催化的、低粘度PAO低聚工艺的总润滑油产率,同时改进了工艺经济性。 With this embodiment, W can be significantly increased, the overall yield of the lubricating oil of low viscosity PAO oligomerization process from metallocene catalyzed, while improving process economics. 来自茂金属低聚的轻质締控副产物的线性特征使得它们对于用作路易斯酸催化的低聚步骤的进料而言是良好选择,因为它们可W 相对于支化締控更容易低聚或共低聚,且制得具有更少链支化和由此更佳的润滑油性能的润滑油基本原料。 Association control light linear features from the metallocene oligomerization byproduct makes them to the feed of the oligomerization step is used as Lewis acid catalyzed terms is a good choice, because they can be branched W with respect to the associated control easier oligomerization or co-oligomerization, and the lubricating oil produced with less chain branching and thereby better performance of the lubricating oil base stock.

[0010] 依据本公开内容,因此,低聚的聚a-締控的制备方法包括使低分子量締控进料在路易斯酸催化剂存在下在低聚条件下进行低聚。 [0010] According to the present disclosure, therefore, poly a- association control preparation comprising low molecular weight oligomeric associated control oligomerization feedstock under oligomerization conditions in the presence of a Lewis acid catalyst. 用作本方法的进料或进料组分的低分子量締控包括轻质締属副产物馈分,其包括源于茂金属催化的PAO低聚工艺的二聚体和轻质馈分;运些締控进料的特征可W为具有120~600的分子量范围和至少25%的末端締控含量。 Low molecular weight is used as the method of controlling association feed or feed components include light byproducts associated feed points genus, which include dimers and light feed fraction derived from metallocene catalyzed PAO oligomerization process; Yun these control features associated feed may be W having a molecular weight range of 120 to 600 and the associated end control content of at least 25%.

[0011] 用于本发明低聚步骤的催化剂包括路易斯酸如=氣化棚或=氯化侣。 [0011] The catalyst used in the oligomerization step of the present invention include Lewis acids such as gasification = Lu = shed or chloride. 通常,路易斯酸催化剂的用量典型地为0.1~lOwt%,且大多数情形下为0.2到3或5wt%,基于締控进料材料的总量。 Typically, the amount of the Lewis acid catalyst is typically 0.1 ~ lOwt%, and in most cases from 0.2 to 3, or 5wt%, based on the total feed material associated control.

[0012] 使用源于茂金属工艺的低分子量a-締控低聚物用于低聚或共低聚的一些优点在于:(1)利用新的、先前浪费的原料方面的灵活性和经济性,该原料可W由特定碳原子数馈分、选定馈分的混合物组成或者,更期望地使用全部、未分馈的PAO蒸馈副产物,采用或不采用a-締控去除;(2)末端亚乙締基双键的存在提供的更大反应性获得具有更加期望性能和高性能特征的液体产物。 Some of the advantages [0012] Use of low molecular weight derived from the metallocene process control associated a- oligomer used in the oligomerization or co-oligomerization in that: (1) the use of new, previously wasted feedstock flexibility and economy aspects the feedstock may be fed W divided by a specified number of carbon atoms, the mixture or composition selected feed points, more desirable to use all of the feed is not divided steam feed PAO byproduct, with or without associated control a- removed; (2 ) the presence of more reactive terminal double bond, ethylene group associated provided to obtain a more desirable properties and performance characteristics of the liquid product.

[0013] 本发明还设及如下实施方案: [0013] The present invention is further provided and the following embodiment:

[0014] 1.低聚的聚a-締控的制备方法,包括在路易斯酸低聚催化剂的存在下使低分子量PAO低聚物进行低聚,该低分子量PAO低聚物通过a-締控进料的茂金属催化低聚制得。 [0014] 1. oligomeric poly a- associated control preparation comprising low molecular weight PAO oligomer is oligomerized in the presence of a Lewis acid oligomerization catalyst, the low molecular weight PAO oligomer is controlled by associative a- metallocene-catalyzed oligomerization of the feed system.

[001引2.实施方案1的方法,其中该低分子量PAO低聚物包含a-締控进料的C化6~C3讯60 低聚物的混合物。 [001 primer 2. The method of embodiment 1, wherein the low molecular weight PAO oligomer comprises a mixture of 6 ~ C3 inquiry C 60 oligomers of a- associated control feed.

[0016] 3.实施方案2的方法,其中该低分子量PAO低聚物包含a-締控进料的C姐16~C3讯60 低聚物的混合物,其分子量范围为120~600、且末端締控含量为全部締属不饱和度的至少25%。 Method [0016] 3. The embodiment of 2, wherein the low molecular weight PAO oligomer comprises a mixture of oligomers News 60 16 ~ C3 C sister a- associated control feed having a molecular weight range of 120 to 600, and the end association control all content associated genera are not at least 25% saturation.

[0017] 4.实施方案3的方法,其中该低分子量PAO低聚物的末端締控含量为全部締属不饱和度的至少50 %。 Method [0017] 4. The embodiment 3, wherein the associated end of the low molecular weight PAO oligomer content control is at least 50% of all genera association unsaturation.

[001引5.实施方案1的方法,其中该a-締控进料包含Cs~Ci4进料。 [001 primer 5. The method of embodiment 1, wherein the feed comprises a- associated control Cs ~ Ci4 feed.

[0019] 6.实施方案1的方法,其中该路易斯酸催化剂包括弗瑞德-克来福特催化剂。 Method [0019] 6. The embodiment 1, wherein the Lewis acid catalyst comprises a Friedel - Crafts catalyst gram.

[0020] 7.实施方案6的方法,其中该弗瑞德-克来福特催化剂包括面化侣或面化棚。 Method [0020] 7. The embodiment 6, wherein the Friedel - Crafts catalysts include gram-surface side of the shed or companion.

[0021 ] 8.实施方案7的方法,其中该面化侣包括=氯化侣。 [0021] 8. The method of embodiment 7, wherein the surface of Lu including Lu = chloride.

[0022] 9.实施方案7的方法,其中该面化棚包括=氣化棚。 [0022] 9. The method of embodiment 7, wherein the surface of the shed includes a gasification = shed.

[0023] 10.实施方案6的方法,其中该路易斯酸催化剂包括面化侣或面化棚与质子促进剂的组合。 Method [0023] 10. The embodiment 6, wherein the Lewis shed combination with a protic promoter of the companion surface or surfaces of the acid catalyst comprises.

[0024] 11.实施方案10的方法,其中该质子促进剂包括水。 [0024] 11. The method of embodiment 10, wherein the protic promoter comprises water.

[0025] 12.实施方案10的方法,其中该质子促进剂包括低级烧醇。 [0025] 12. The method of embodiment 10, wherein the protic promoter comprises a lower alcohol burning.

[0026] 13.实施方案1的方法,其中该路易斯酸催化剂的用量为0.2~5wt%,基于低分子量PAO低聚物进料的总量。 Method [0026] 13. The embodiment 1, wherein the amount of the Lewis acid catalyst is 0.2 ~ 5wt%, based on the total amount of low molecular weight PAO oligomer feed.

[0027] 14.实施方案1的方法,其中使该低分子量PAO低聚物在路易斯酸催化剂存在下与a-締控共聚单体进行共低聚。 [0027] 14. The method of embodiment 1, in which the low molecular weight PAO oligomer and co-oligomerization control a- associative comonomer in the presence of a Lewis acid catalyst.

[002引15.实施方案14的方法,其中该a-締控共聚单体包括Cs~Cwa-締控。 [002 primer 15. The method of embodiment 14, wherein the control a- associative comonomers include Cs ~ Cwa- associated control.

[0029] 16.实施方案1的方法,其中在该路易斯酸催化剂存在下的低聚在0~75°C的溫度下进行。 [0029] Embodiment 16. The method of claim 1, wherein the oligomerization catalyst in the presence of the Lewis acid at a temperature of 0 ~ 75 ° C.

[0030] 17.-种低聚的聚a-締控的制备方法,其包括在路易斯酸低聚催化剂存在下使(i) C40-締属馈分、(ii )C8~Cwa-締控进行共低聚,其中该C40-締属馈分衍生自低分子量PAO低聚物馈分,该低分子量PAO低聚物馈分通过Cs~Cwa-締控进料的茂金属催化低聚制得并且包含该a-締控进料的C姐16~C30也0低聚物,分子量范围为120~600的混合物,和包含全部締属不饱和度至少50%的末端締控含量。 [0030] Poly-controlled method for preparing a- association 17.- oligomeric species, which comprises (i) C40- associated feed points genus presence of a Lewis acid oligomerization catalyst so, (ii) C8 ~ Cwa- associated control performed co-oligomerization, wherein the feed points C40- association derived from a metal of low molecular weight PAO oligomer feed points, the low molecular weight PAO oligomer feed through sub-Cs ~ Cwa- associated control feed and metallocene-catalyzed oligomerization prepared comprising the a- C sister associated feed control also 0 16 ~ C30 oligomer, a mixture of molecular weight range of 120 to 600, and containing terminal association control all content associated unsaturation of at least 50%.

[0031] 18.实施方案17的方法,其中该路易斯酸催化剂包括由质子促进剂促进的面化侣或面化棚。 [0031] 18. The method of embodiment 17, wherein the Lewis acid catalyst comprises a promoted proton accelerator of the companion surface or surfaces of the shed.

[0032] 19.实施方案18的方法,其中该质子促进剂包括水、低级烧醇、质子酸或醋。 [0032] 19. The method of embodiment 18, wherein the protic promoter comprises water, a lower alcohol burn, protonic acid or vinegar.

[0033] 20.实施方案17的方法,其中该路易斯酸催化剂的用量为0.2~5wt%,基于低分子量PAO低聚物进料和Cs~Cwa-締控共聚单体的总量。 [0033] 20. The method of embodiment 17, wherein the Lewis acid catalyst in an amount of 0.2 ~ 5wt%, based on the total amount of low molecular weight PAO oligomer feed and Cs ~ Cwa- associative control comonomers.

[0034] 21.-种润滑油沸程范围内的低聚的聚a-締控的制备方法,包括在路易斯酸低聚催化剂存在下使低分子量締属进料进行低聚,该低分子量締属进料包含至少25 %的下式的亚乙締基化合物: Poly a- association control method of preparing the oligomeric [0034] 21.- species lube boiling range, including low molecular weight in the presence of a Lewis acid oligomerization catalyst feed genus associated oligomerization, association of the low molecular weight genus ethylene associative compound of the formula feed comprises at least 25%:

[0035] r1r2c = CH2 [0035] r1r2c = CH2

[0036] 其中Ri和R2,它们可W相同或不同,一起具有6~40个碳原子且Ri为1~24个碳原子的控基,R2为Ri或H。 [0036] wherein Ri and R2, which may be the same or different W, together have from 6 to 40 carbon atoms, and Ri is a control group having 1 to 24 carbon atoms, R2 of or Ri is H.

[0037] 22.实施方案21的方法,其中Ri和R2-起具有16~30个碳原子。 Method [0037] 22. The embodiment of 21, wherein Ri and R2- having from 16 to 30 carbon atoms.

[003引23.实施方案22的方法,其中R哺R2各自具有8~11个碳原子。 [003 primer 23. The method of embodiment 22, wherein R feeding R2 each have 8 to 11 carbon atoms.

[0039] 24.实施方案21的方法,其中该低分子量締属进料包含至少50wt%的式RiR2C = C出的亚乙締基化合物。 [0039] The method of 21, wherein the low molecular weight ethylene genus association associative compound 24. The embodiment of the feed formula comprises at least 50wt% of RiR2C = C out.

[0040] 25.实施方案24的方法,其中该低分子量締属进料包含至少60wt%的式RiR2C = C出的亚乙締基化合物。 The method of Scheme 24 [0040] 25. The embodiment, wherein the low molecular weight associative genus feed formula comprises at least 60wt% of ethylene RiR2C = C out associative compound.

[0041] 发明详述 [0041] DETAILED DESCRIPTION

[0042] 本文发明详述和权利要求中的所有数值由"大约"或"近似"所示值来修饰,且考虑了本领域技术人员应预期的实验误差和偏差。 [0042] All numerical values ​​and claims of the invention detailed herein are modified by the values ​​shown in "about" or "approximately", and in view of the skilled artisan to be expected experimental error and deviation.

[0043] 締控进料 [0043] associated control feed

[0044] 本方法中使用的締控进料包括轻质締属副产物馈分,其包括源于茂金属催化的PAO低聚工艺的二聚体和轻质馈分。 [0,044] used in the present process comprises feeding the association control light byproducts associated feed points genus, which include those derived from a metallocene-catalyzed PAO oligomerization process dimers and light feed points. 运些中间体轻质馈分通常可W表征为C42-(通常C40-)締属蒸馈馈分,其包含源于原始a-締控原料的高反应性低聚物的混合物;该馈分主要含有C皿6~C30也0低聚物(平均C20H40),其显示的分子量范围为120~600、典型地为140~560(平均200)且含有的末端締控含量为全部締属不饱和度的至少25%。 These intermediate feeding operation light W may be generally characterized as sub-C42- (typically C40-) feeding steam feed points associated genus, comprising high reactivity due to the original control association a- oligomer mixture starting material; the feed points dish containing primarily C 6 ~ C30 also 0 oligomer (average C20H40), which shows the molecular weight range of 120 to 600, typically a terminal association control content from 140 to 560 (mean 200) and is contained in all the associative unsaturated at least 25% of the degrees. 实际上,该混合物的亚乙締基含量可W为至少50%,例如60或者甚至80%,取决于茂金属催化剂和低聚条件。 Indeed, the ethylene content of the mixture associative group W may be at least 50%, for example 60 or even 80%, depending on the metallocene catalyst and oligomerization conditions. a-締控二聚体/ =聚体馈分中高含量的亚乙締基締控与相应更少的其它类型締属不饱和度是独特的,运点得到IH和13C-NMR的证实且给本方法带来区别,本方法利用运些独特締控作为随后采用路易斯酸催化剂的低聚的原材料W制得具有有益性能的润滑油范围产物。 a- associated control dimer / multimer = feed points in the association of high levels of ethylene-based associative control and other types of association corresponding to less unsaturation is unique, and the operation point obtained IH and 13C-NMR confirmed to this method brings the difference, the present method utilizes these unique operation associated subsequently employed as control lube range product material W Lewis acid catalyst oligomeric produced with advantageous properties.

[0045] 用作进料的茂金属衍生的中间体通过使用茂金属低聚催化剂的a-締控进料低聚来制备。 [0045] The metallocene derivative used as the feed intermediates by using a metallocene oligomerization catalyst feed oligomerization control associated a- prepared. 运种初始低聚步骤中使用的a締控进料典型地是4~24个碳原子、通常6~20个且优选8~14个碳原子的a-締控单体,如1-下締、1-己締、1-辛締、1-癸締、1-十二碳締、和1-十四碳締。 The initial oligomerization step transported species used in a feed control association is typically 4 to 24 carbon atoms, usually 6 to 20 and 8 a- associative monomer is preferably controlled to 14 carbon atoms, such as 1-lower association , 1-associative, 1-octene association, 1-decene association, association 1-dodecene, 1-tetradecene and association. 具有偶数碳原子的締控是优选的,因为它们是线型a締控,尽管能够使用在距离末端双键至少两个碳原子处具有烷基取代基的支链締控。 Control associated with even number of carbon atoms are preferred, because they are associated a control line, although the terminal double bond can be used at a distance of at least two carbon atoms having a branched alkyl substituent group associated control. 运些1-締控可W与相同分子量范围内的其它单体共低聚。 Intracapsular some other monomer may be 1- W control associated with the same molecular weight range of co-oligomerization. 运些原材料采用茂金属催化剂来进行低聚,由此制得从低分子量二聚体和=聚体(其形成用于本发明路易斯酸催化步骤的主要进料)W及润滑油沸程内的更高分子量低聚物(其直接用作润滑油基本原料)延伸的一系列产品。 These raw materials are transported to a metallocene oligomerization catalyst, thereby obtaining a low molecular weight dimers and from = mers (which form the main feed for the Lewis acid catalyzed step of the present invention) and the lubricating oil boiling range W higher molecular weight oligomer (which is directly used as lube base stock) extending range of products. 优选地将初始进料締控进行处理W除去催化剂毒物,如过氧化物、氧、硫、含氮有机化合物、和/或烘属化合物,如WO 2007/011973中所述。 Preferably, the initial feed control association processing W remove catalyst poisons, such as peroxides, oxygen, sulfur, a nitrogen-containing organic compound, and / or drying metal compounds, as described in WO 2007/011973. 认为运种处理提高了催化剂生产力,典型地大于5倍,且有利情形下大于10倍。 Yun treatments that improve catalyst productivity, typically greater than 5-fold and 10-fold greater than in favorable circumstances. 来自运些a締控原材料的最低分子量低聚物典型地具有范围为Cs~C30、大多数情形下Cl6~C3G的碳原子数。 These run from a lowest molecular weight material associated control oligomer typically having in the range of Cs ~ C30 carbon atoms, most cases of Cl6 ~ C3G. 运些小低聚物通常通过分馈与具有大于C3G、例如C4G和更高碳原子数的更高低聚物相分离,其典型地用作高性能润滑油基本原料。 Some small oligomers are usually transported by the feed points of C3G with greater than, e.g. C4G higher and the number of carbon atoms higher oligomers phase separation, which is typically used as high-performance lubricant base stock.

[0046] 使用茂金属催化剂的初始低聚步骤在适合于所选a締控进料和茂金属催化剂的条件下进行。 [0046] The initial oligomerization step is carried out using a metallocene catalyst under conditions suitable for associating a selected control feed and metallocene catalysts. 优选的茂金属催化的a締控低聚工艺描述于WO 2007/011973,关于进料、茂金属催化剂、工艺条件和产品表征的详细内容参考该文献。 a control association preferred metallocene-catalyzed oligomerization process are described in WO 2007/011973, concerning the feed, the details of a metallocene catalyst, process conditions, and product characterization which reference. 由该工艺制得的且用作本发明低聚步骤中进料的轻质締属低聚物可W适宜地通过蒸馈与茂金属低聚步骤之中获得的a締控低聚物的粗混合物分离,其中依据要用作润滑油基本原料的馈分或者要用作路易斯酸催化工艺步骤进料的馈分来设定切割点。 Obtained from the process and used as the oligomerization step of the present invention, the light feed associative genus crude oligomer may be suitably W fed by the metallocene oligomerization step was distilled into association obtained in a control oligomers the mixture was separated, which is used as feed according to the basic points to be used as raw material oil or Lewis acid catalyzed step process feeding feed cut point set points. 如WO 2007/011973中所述,选择用于润滑油基本原料馈分的PAO低聚物是液体,其烙点不高于(TC,倾点小于(TC,典型地小于-45°C或甚至更低,例如小于-75°C,优选地具有1.5~20cSt的KViQQ,其在许多情形下依据期望的产品规格来进行选择,如范围为1.5~lOcSt。通过Noack挥发性试验(ASTM D5800)测量的润滑油范围馈分的挥发性典型地为25wt%或更低,优选为14wt%或更低。润滑油馈分的漠值典型地为1.8或更大,在用作润滑油基本原料之前通过氨化过程使其降低。分子量范围方面,选择用作润滑油基本原料的馈分典型地对于C20和更高的控具有80%或更大的选择性,优选地对于C20和更高的控为85%或更大、优选为90%或更大、更优选为95%或更大、优选为98%或更大、优选为99 %或更大。对于C20和更低的控的相应选择性通常为50 %或更低,优选为40 %或更低,例如20%或更低,10%或更低。 As described in WO 2007/011973, for selecting the feed points of the lube base stock is a PAO oligomer liquid, which branded point of not higher than (the TC, pour point less than (the TC, typically less than -45 ° C, or even less, such as less than -75 ° C, preferably having KViQQ 1.5 ~ 20cSt, which is selected according to the desired specifications in many situations, such as in the range of 1.5 ~ lOcSt. by the Noack volatility test (ASTM D5800) measured the lube range feed points volatile typically 25wt% or less, preferably 14wt% or less. desert feeding value of the lubricating points is typically 1.8 or more, prior to use as lube base stock by so reducing amination procedure molecular weight ranges, the feed points are typically selected for use as lubricating oil base stock for the control of C20 and higher selectivity of 80% or more, preferably for the control of C20 and higher 85% or more, preferably 90% or more, more preferably 95% or more, preferably 98% or more, preferably 99% or more corresponding lower selectivity to C20 and controlled is generally 50% or less, preferably 40% or less, such as 20% or less, 10% or less.

[0047] WO 2007/011973工艺中使用的茂金属催化剂是非桥连的、取代的双环戊二締基过渡金属化合物。 [0047] The non-bridged metallocene catalyst used in the process of WO 2007/011973 connected, glutaric associative substituted bicyclic group transition metal compound. 一种优选类别的催化剂是高取代的茂金属,其获得高催化剂生产力且具有低产物粘度。 A preferred class of catalysts are highly substituted metallocenes, which obtain high catalyst productivity and have a low viscosity product. 另一优选类别的茂金属是非桥连且取代的环戊二締类,包括非桥连的和取代的或未取代的巧和/或巧。 Another preferred class of metallocenes and non-bridged substituted cyclopentadienyl-based association, including unbridged and substituted or unsubstituted clever and / or clever. 任选地,用于茂金属组分的活化剂可WW过渡金属化合物与活化剂的摩尔比典型地10:1~0.1:1来使用例如甲基侣氧烧(MAO);如果有机侣化合物例如烷基侣化合物用作活化剂,烷基侣化合物与过渡金属化合物的摩尔比范围可W为1:4~4000:1。 Optionally, an activator for the metallocene component may WW transition metal compound to activator molar ratio is typically 10: 1 to 0.1: 1 is used to burn an oxygen companion e.g. methyl (of MAO); companion if the organic compound e.g. Lu alkyl compound used as the activator, the molar ratio of the transition metal compound companion alkyl compound may be W is 1: 4 to 4000: 1. 低聚条件典型地要求氨气W345kPa(50psi)或更低的分压存在,基于反应器的总压,典型地为化化(Ipsi)~34化化巧Opsi),(优选为20kPa(:3psi)~275kPa(40psi),例如35kPa(5psi) ~210k化psi(30),或者17化化(25psi)或更低,优选为70kPa(10psi)或更低。氨气的存在浓度通常为10~10 000重量ppm,优选为25~7500ppm,例如25~SOOOppm,其中a-締控单体进料为10体积%或更多,基于催化剂/活化剂/助活化剂溶液、单体、和反应中存在的任意稀释剂或溶剂的总体积。反应停留时间典型地为至少5分钟,且反应区中溫度在反应期间控制在不超过l〇°C。茂金属催化剂组分、活化剂W及典型的和优选的反应条件与产品参数均描述于WO 2007/011973,关于运些描述参考该文献。 Oligomerization conditions typically require ammonia W345kPa (50psi) or lower partial pressure, based on the total reactor pressure, typically of the of (Ipsi) ~ 34 of the coincidence of OPSI), (preferably 20kPa (: 3psi ) ~ 275kPa (40psi), for example, 35kPa (5psi) ~ 210k of psi (30), of 17 or of (25psi) or less, preferably 70kPa (10psi) or less. ammonia gas is generally present in a concentration from 10 to 10000 ppm, preferably of 25 ~ 7500ppm, for example, 25 ~ SOOOppm, wherein the control a- associative monomer feed is 10 vol% or more, catalyst / activator / co-activator solutions, monomers, and based on the reaction the total volume of the diluent or solvent is present in any of the reaction residence time is typically at least 5 minutes, and the temperature of the reaction zone during the reaction was controlled at no more than l〇 ° C. the metallocene catalyst component, activator and typical W and preferred reaction conditions and product parameters are described in WO 2007/011973, concerning the operation described with reference to these documents.

[0048] 替换形式的茂金属催化的a-締控低聚工艺(其可W获得适合作为本公开内容的第二低聚步骤进料的二聚体馈分)描述于US 6,548,724W及该专利中引用文献中的其它茂金属催化的低聚工艺,关于运些替换形式工艺的详细内容可参考该文献。 a- association metallocene catalyzed oligomerization process control [0048] alternative form (which may be W is obtained as a dimer of the present disclosure for the second oligomerization step of feeding a feed point) and described in the patent US 6,548,724W other references metallocene catalyzed oligomerization process literature, details of the operation of these processes may be alternative forms which reference. 可W获得适合作为本公开内容的第二低聚步骤进料的二聚体馈分的其它茂金属聚合工艺描述于胖02007011459、胖02007011462、^及115 5,017,299和5,186,851,关于运些茂金属催化的低聚工艺的信息也参考运些文献。 W can be obtained dimers are suitable as feeding points of the present disclosure second oligomerization step of feeding the other metallocene polymerization processes described in fat 02007011459, 02007011462 fat, ^ 115 and 5,017,299 and 5,186,851, some operation on the metallocene catalytic oligomerization process information is also transported some literature reference. 源于运些使用Q-締控原材料的茂金属低聚工艺的轻质締控PAO低聚物馈分可W用作利用运些轻质締属副产物作为进料组分的本发明方法中的进料。 These associative operation from the control starting material used Q- metallocene oligomerization process of light associated control PAO oligomer feed points can be transported using W as a byproduct of these light association method of the present invention, metal components in the feed feed.

[0049] 用作本发明方法的进料的二聚体具有至少一个碳碳不饱和双键。 [0049] The method of the present invention is used as a dimer of the feed having at least one carbon-carbon unsaturated double bond. 由于茂金属工艺的非异构化聚合机理特征,不饱和度通常或多或少居中地位于构成该二聚体的两个单体单元连接处。 Wherein the polymerization mechanism of the non-metallocene isomerization process, the unsaturation is generally more or less centrally located two monomer units constituting the dimer connections. 如果初始茂金属聚合步骤使用单一的1-締控进料来制备O-締控均聚物,不饱和度将居中地定位,但是如果使用两种1-締控共聚单体来形成茂金属共聚物,双键位置可W 依据所用两种共聚单体的链长而偏离中屯、。 If the initial polymerization step to prepare the metallocene O- associated control associated with a single 1-homopolymer feed control, the degree of unsaturation centrally located, but if two control 1- associative copolymerizable comonomers formed a metallocene was based on the W position of double bonds may be two kinds of copolymerizable monomer chain lengths deviate from the village with. 任意情形下,运种双键具有乙締基或亚乙締基特性。 In any case, having a double bond transported species ethylene ethyl group or association of associative Kit. 末端亚乙締基由式RaRbC = C此表示,当Rb = H时称作乙締基。 Ethylene associative terminal group represented by the formula RaRbC = C express called associative ethyl group when Rb = H. 不饱和度数量可W依据ASTM Dl 159的漠值测量或等价方法定量测定,或者依据质子或碳-13NMR定量测定。 W be the number of unsaturation value according to ASTM Dl 159 desert or equivalent measuring quantitatively determined, or measured in accordance with quantitative proton or carbon -13NMR. 质子NMR 光谱分析也可W区分和量化締属不饱和度类型。 Proton NMR spectroscopic analysis can also differentiate and quantify the association W unsaturation type.

[0050] 构成本发明低聚工艺締控进料的至少25%的特征亚乙締基化合物由此可W定义为下式的不饱和控: [0050] constituting at least 25% of the associative compound wherein ethylene oligomerization process associated feed control of the present invention may thus be defined as W of the formula unsaturated control:

[0051] r1r2c=c 出 [0051] r1r2c = c a

[0052] 其中Ri和R2,它们可W相同或不同,一起具有6~40个碳原子且Ri为1~24个碳原子的控基,R2为Ri或H。 [0052] wherein Ri and R2, which may be the same or different W, together have from 6 to 40 carbon atoms, and Ri is a control group having 1 to 24 carbon atoms, R2 of or Ri is H. 典型地,Ri和R2-起具有16~30个碳原子,优选为8~11个碳原子,且在由单一单体制备的二聚体的情形下,Ri和R2相同。 Typically, Ri of R2- and having from 16 to 30 carbon atoms, preferably 8 to 11 carbon atoms, and in the case of a dimer prepared from a single monomer, and Ri of the same as R2. 优选的二聚体中,Ri和R2各自具有7~13个碳原子。 Preferred dimer, Ri and R2 each having 7 to 13 carbon atoms.

[0053] 源于茂金属低聚工艺的轻质締控(主要为二聚体和=聚体)馈分可W用作本发明方法中的唯一进料材料,或者其可W用作締属进料组分之一与用作茂金属低聚步骤的締控原材料类型的O-締控一起。 [0053] The light from the metallocene oligomerization process control association (mainly dimer and = mer) W can be used as the sole feed points feed material in the method of the present invention, or it may be used as an associative W genus one is used as feed components and associated control of the metallocene oligomerization step of the raw materials with controlled association type O-. 具有线性或支化结构的O-締控或其它内部締控、或者它们的混合物,可W与低分子量Q-締控低聚物一起用作进料。 Having a linear or branched structure, or other internal control O- association controls association, or mixtures thereof, W can be controlled with a low molecular weight oligomer as associative Q- fed together. 由此,茂金属轻质締属Q-締控低聚物可W用作例如与6~24个碳原子、通常6~20且优选8~14个碳原子的单体a-締控结合的进料, 优选締控与碳计数締控(如1-癸締、1-辛締、1-十二碳締、1-己締、1-十四碳締、1-十八碳締或其混合物)。 Accordingly, the light associated metal metallocene Q- oligomer can be controlled associative W used, for example, the associative monomers a- control generally 6 to 20 and preferably from 8 to 14 carbon atoms in combination with 6 to 24 carbon atoms, feed, preferably a carbon count associated control and associated control (e.g., 1-decene associative, 1-octene association, association of 1-dodecene, 1-association, the association 1-tetradecene, 1-octadecene, or associated mixture). 如果期望获得最佳润滑油性能则优选是线性Q-締控,但是也能够使用在距离末端双键至少两个碳原子处含有烷基取代基的支链締控。 If it is desired to obtain optimal performance of the lubricating oil is preferably linear Q- association control, but can also be used from the terminal double bond in the carbon atom containing at least two alkyl substituent branches associated control. 可W使用的轻质a-締控低聚物的比例可能在实际操作中通过原材料可用性W及对于产物期望的参数来设定,产物本身也取决于本发明方法的路易斯酸催化低聚步骤中采用的反应条件。 A- a light control ratio associated oligomer may be used in W and W may be the availability of the product for the desired parameters set by the material in the actual operation, the product itself is dependent on the method of the present invention the Lewis acid catalyzed oligomerization step the reaction conditions employed. 典型比例为90:10~10:70或10:90,且更通常地为80: 20~20:80重量,但是通常轻质a-締控低聚物(二聚体/S聚体)馈分将构成締属进料材料的至少50%重量,运是因为最终产品的性能(部分地取决于原材料) 有利地受到提高轻质低聚物馈分的比例的影响。 The typical ratio is 90: 10 ~ 10: 70 or the 10:90, more typically from 80: 20 to 20: 80 by weight, but generally associated control light a- oligomer (dimer / S mer) feed hours, associated metal constituting the feed material is at least 50% by weight, because the transport properties of the final product (in part depending on the raw material) is advantageously affected by the proportion of the oligomer feed to improve the light points. 締控进料中关于轻质低聚物馈分的优选比例由此为至少50%,且更优选为至少60%,或70%,或80%重量。 Preferably associated control feed ratio of the light thus divided oligomer feed is at least 50%, more preferably at least 60%, or 70%, or 80% by weight.

[0054] 路易斯酸催化的低聚 [0054] The Lewis acid catalyzed oligomerization

[0055] 轻质締控馈分的低聚在包含路易斯酸的催化剂存在下进行。 [0055] The light control associated feed points oligomerization in the presence of a catalyst comprising a Lewis acid under. 可W用于締控低聚反应的路易斯酸催化剂包括通常用作弗瑞德-克来福特催化剂的金属和类金属面化物,其适宜实例包括AlCl3、B的、AlBr3、TiCl3、和TiCU,它们按自身使用或者与质子促进剂一起使用。 Lewis acid catalysts may be used in association W controlled oligomerization reaction include commonly used as Friedel - Friedel-Crafts catalyst metals and metal surfaces thereof, suitable examples thereof include AlCl3, B's, AlBr3, TiCl3, and TiCu, they used by itself or in combination with a protic promoter. 也可W使用固体路易斯酸催化剂,如合成或天然沸石,酸性粘±,聚合物酸性树脂,无定形固体催化剂如娃石-氧化侣,和杂多酸如错酸鹤、钢酸鹤、饥酸鹤、憐鹤酸盐和钢鹤饥错酸盐(例如WOx/化化,W化/Mo化),尽管运些催化剂通常不象用于传统PAO低聚工艺中的金属和类金属面化物那样经济上有利。 W may also be a solid Lewis acid catalyst, such as synthetic or natural zeolites, acidic ± viscosity, polymeric acidic resin, an amorphous solid catalysts such as baby Stone - Lu oxide, and a heteropolyacid such as wrong acid crane, crane steel acid, hunger acid crane, crane pity salts and hunger wrong steel crane salt (e.g. WOx / oriented technology, W of / Mo based), although these catalysts typically run for not as in conventional PAO oligomerization process metals and metal compounds as surface economically advantageous. 通常,低聚或共低聚工艺中使用基于总进料为0.1~lOwt%且优选0.2~3或5wt %的酸催化剂。 Generally, the oligomerization or co-oligomerization process based on total feed is 0.1 ~ lOwt% and preferably from 0.2 to 3, or 5wt% of an acid catalyst.

[0056] 最经常用于源于茂金属低聚的轻质締控馈分低聚的路易斯酸催化剂是典型用于传统PAO低聚工艺的金属和类金属面化物催化剂,主要是S氯化侣和S氣化棚,其中优选后者。 [0056] The most frequently used for light from the metallocene oligomerization feed control division association oligomerization catalyst is a metal Lewis acid and the metal surface of the catalyst is typically used in the conventional PAO oligomerization process, mainly companion chloride S S gasification and shed, the latter being preferred. 但是,S氣化棚并不特别适合用作低聚催化剂,除非其与质子促进剂组合使用。 However, S is not particularly suitable for use as a gasification shed oligomerization catalyst, unless it is used in combination with a proton accelerator. 对于BF3 催化的締控低聚工艺而言,各种运类促进剂是沿用已久的,且包括材料诸如水,醇类如低级(Ci-Cs)烧醇(包括乙醇、异丙醇或下醇),酸类,可W为有机酸例如簇酸或其酸酢如乙酸、丙酸、或下酸或者乙酸酢,或者无机酸如憐酸(如US 3,149,178中所述),醋如乙酸乙醋(如US6,824,671中所述),醇烷氧基化物如二醇酸,例如乙二醇单甲基酸(2-甲氧基乙醇)或丙二醇单乙基酸,或者衍生自混合C2~C24、优选C2~Cl8且最优选Cs~Cl2直链醇的乙氧基化物(如US 5,068,487中所述),和酸类如二甲基酸、二乙基酸或甲基乙基酸,酬类,醒类和烷基面化物。 For associative BF3 catalyzed oligomerization process control, various transport accelerators are well established, and include materials such as water, alcohols, such as lower (Ci-Cs) burning alcohol (including ethanol, isopropanol or a lower alcohol), acids, organic acids such as W may be the cluster acid or an acid such as vinegar acetic acid, propionic acid or vinegar or acetic acid or inorganic acids such as pity (e.g. described in US 3,149,178), such as ethyl acetate vinegar vinegar (as described in US6,824,671), alcohol alkoxylates such as glycolic acid, such as ethylene glycol monomethyl acid (2-methoxyethanol) or propylene glycol monoethyl acid, or derived from a mixed C2 ~ C24, preferably C2 ~ Cl8 and most preferably Cs ~ Cl2 linear alcohol ethoxylates (as described in US 5,068,487), acid, and acids such as dimethyl, diethyl or methylethyl acid acid, reward class, and alkyl wake surface thereof. 质子促进剂与=氣化棚形成催化剂络合物,且充当低聚催化剂的是该络合物;运种络合物通常含有吸收在该混合物中的过量=氣化棚。 = Proton accelerator and a gasification catalyst complex is formed shed, and acts as oligomerization catalyst is the complex; complex operation kind generally contain excessive absorption in the mixture of vaporized = shed.

[0057] 在路易斯酸催化剂存在下低聚的、源于茂金属低聚步骤的低分子量a-締控低聚物典型地具有范围为120~600的数均分子量,末端締控含量大于25%。 [0057] in the presence of a Lewis acid catalyst under oligomerization, from the metallocene oligomerization step of the low molecular weight oligomer a- associated control typically have a range of number average molecular weight of 120 to 600, the terminal association control content greater than 25% . 通常优选在进料中具有更高数量的末端締控。 Is generally preferred in the feed have a higher number associated control terminal.

[0058] 在路易斯酸催化低聚步骤中可能使用溶剂或稀释剂,但是如果所用催化剂体系是液体,那么该液体也可W起到反应溶剂或稀释剂的作用,使得无需额外的溶剂或稀释剂。 [0058] may be used in the Lewis acid catalyzed oligomerization step a solvent or diluent, but if the catalyst system is a liquid, then the liquid W may also function as a reaction solvent or diluent, such that no additional solvent or diluent . 但是如果期望时,可W存在对所选催化剂体系无反应性的额外液体,例如为了控制反应混合物的粘度或者为了通过带有冷凝蒸汽回流的蒸发而带出反应热。 However, if desired, there may be additional liquid W catalyst system selected anergy, for example to control the viscosity of the reaction mixture by evaporation with or to reflux the condensed vapor out of the heat of reaction. 控如烧控和芳控例如己烧或甲苯适用于运个目的。 The controlled burning control and aryl burn control hexyl e.g. toluene or suitable transport object. 由此,轻质O-締控低聚物反应物,按自身或是与额外O-締控共进料一起,可W直接在添加或不添加溶剂或稀释剂的催化剂体系存在下进行低聚。 Accordingly, the light control O- associated oligomer reactants, by itself or with an additional co-feed with controlled association O-, W can be performed directly in the presence of oligomeric or without the addition of a solvent or diluent, catalyst system . 在使用气态催化剂如=氣化棚时通常反应在封闭环境中,通常在惰性气氛例如氮气下进行。 When using a catalyst such as a gaseous gasification = shed Typically the reaction is usually carried out under an inert atmosphere such as nitrogen in a closed environment.

[0059] 实际操作中路易斯酸催化低聚反应的溫度有利地在-10°C至300°C、优选(TC~75 °C之内变化。该体系可W在大气压力下操作,因为该体系典型地在通常用于该工艺的溫度下显示低蒸气压。但是如果期望保持封闭反应环境、例如自生压力下,可W在溫和压力下操作。使用固体路易斯酸作为催化剂时,该低聚通常采用催化剂固定床W下流方式来进行,尽管替换形式的操作、例如在揽拌槽反应器中也是可能的。 [0059] In practice Lewis acid catalyzed oligomerization reaction temperature is advantageously at -10 ° C to 300 ° C, a change (within the TC ~ 75 ° C is preferred. The system can be operated at atmospheric pressure W, because the system when typically exhibit a low vapor pressure at temperatures typically used for this process. However, if desired the reaction environment is kept closed, under autogenous pressure, for example, W may be operated under mild pressure a solid Lewis acid as the catalyst, the oligomerization usually W downflow fixed catalyst bed mode is performed, although alternative forms of operation, for example, football stirred tank reactor is also possible.

[0060] 低聚反应完成之后,催化剂活性可W通过添加水或稀释含水碱如5wt%化0田容液来泽灭。 [0060] After completion of the oligomerization reaction, the catalyst activity by adding water or W may be diluted with an aqueous base such as 0 5wt% of the liquid containment field to destroy Ze. 可W将有机层分离并蒸馈W除去基本原料之外的组分。 W may be separated and the organic layer was distilled to remove the components outside the basic feed material W. 使用促进的BF3催化剂时, 如果在反应结束时未去活化,可W将气态BF3和促进剂再循环。 When using promoted BF3 catalyst, if it is not deactivated at the end of the reaction, gaseous BF3 can be and W accelerator recycled. 使用固体催化剂时,如果反应未在固定床中进行,简单过滤就是将催化剂与低聚物产物分离所需的全部操作。 When using a solid catalyst, if the reaction is not carried out in a fixed bed, simple filtration is all that is required of the catalyst with the oligomer product separation. 随后可W将低聚物产物分馈W除去任意未反应的轻质締控,并将在期望沸程内的低聚物送到氨化过程W除去残留不饱和度。 W can then be fed oligomer product fraction W remove any unreacted associated light control, and in the desired boiling range oligomer amination procedure W to remove residual unsaturation.

[0061 ] 低聚物产物 [0061] The oligomer product

[0062] 由巧金屋化聚物中间化化成化聚物产物前LU由血下元意图来表示; [0062] Qiao ago by Kanaya homopolymer of intermediate product into a homopolymer represented by the blood LU roadway intended;

[0063] [0063]

Figure CN105925340AD00091

[0064] 在此情况下,所示的那部分最终低聚物产物是具有高支链结构的PAO反应物的S 聚体,可W预期其构成低挥发性、低倾点和高粘度指数的润滑油基本原料。 S-mer [0064] In this case, the portion shown in the final PAO oligomer product having a high reactant branched structure can be expected to constitute a W lubricating low volatility, low pour point and high viscosity index The basic raw materials. 但是,依据原材料的碳原子数和所选反应条件,该产物可W是二聚体、=聚体、或者具有通过反应物的双键位点连接的连续单元的更高低聚物。 However, according to the number of carbon atoms of the starting material and the reaction conditions selected, the product may be a dimer W, = mer, or higher oligomers having consecutive units are connected by a double bond sites of the reactants. 链支化程度主要由反应物确定,使得如果茂金属制得的PAO中间体本身具有一定链支化程度时(如通过使用支链締控作为茂金属低聚体系的进料),源于路易斯酸催化反应的最终产物中将存在额外的支化。 The degree of chain branching is mainly determined by the reactant, such that if the metallocene prepared PAO intermediate itself has a certain degree of chain branching (such as metallocene oligomerization system by using a feed control association branched), derived from Lewis the final product in the presence of acid-catalyzed reactions of additional branching. 但是,如上所述,茂金属低聚物主要是具有中屯、締属双键(在此发生加成)的线性低聚物。 However, as described above, the metallocene oligomer having the main village, associative linear oligomers double metal (here an addition) of.

[0065] 源于路易斯酸催化低聚步骤的低聚物产物W它们的流变学性能、同时具有低倾点和高粘度指数的组合著称。 Composition [0065] derived from the Lewis acid catalyzed oligomerization step of the oligomer product W rheological properties thereof, while having a low pour point and high viscosity index is known. 倾点通常低于-40°C,甚至在粘度QO(TC)为20或更高的更高分子量低聚物的情形下也是如此。 Pour point is usually below -40 ° C, even in viscosity QO (TC) of 20 or more higher molecular weight oligomers case. 倾点(ASTM D97或等价方式)通常范围为-40至-55°C,通常低于-45°C。 A pour point (ASTM D97 or equivalents) is typically in the range of -40 to -55 ° C, typically below -45 ° C. 粘度指数(ASTM D2270)通常高于130,且通常范围为135~150。 Viscosity index (ASTM D2270) is generally higher than 130 and typically in the range of 135 to 150. 产物粘度可W通过低聚条件、特别是反应溫度和反应时间的变化来改变,其中更高溫度和持续时间获得更高分子量/更高粘度产品。 W may be oligomerized product viscosity conditions, notably the reaction temperature and reaction time changes to change, where higher temperatures and duration of higher molecular weight / higher viscosity products. 该产品的润滑剂(C30+)馈分典型地是4-300cSt(10(TC)材料,但是对于在其中需要低粘度基本原料的润滑油中使用而言也可W获得极低粘度产品2-4cSt (lOCrC)。容易获得在经济上重要的4-6cSt(10(TC)范围内的产品,使得可能通过使用源于茂金属低聚的二聚体/ =聚体副产物馈分(先前不能包含在润滑剂馈分之中)改善总体润滑剂产率(基于a-締控原材料)。大多数情形下,对于低粘度、高品质润滑剂的需求趋向于范围4-40,例如4-30或6-40cSt(l〇〇°C)基本原料,且运些容易W本发明低聚工艺的产物的形式获得。产物分子量范围典型地为420W上,大多数情形下在600W上且典型地对于粘度范围为25-30cSt(10(TC)的低聚物而言一直延伸到2000。更高分子量和相应粘度可W通过反应条件的适宜选择来实现。多分散指数(PDI)数值典型地为1.15~1.4,该范围之内的更高数值与更高分子量低聚物相关,其中不 The lubricant products (C30 +) is typically a sub-feeding 4-300cSt (10 (TC) material, but for the lubricating oil base stocks which require low viscosity may also be used in terms of very low viscosity products obtained W 2-4cSt (lOCrC). readily obtained in economically important product 4-6cSt range (10 (TC), that may result from the metallocene oligomerization by using a dimer / dimer byproduct = feed points (previously not contain improvement of the overall yield of the lubricant in the lubricant feed points) (a- associated control based materials). in most cases, for low viscosity, demand for high quality lubricants tend to range 4-40, 4-30 or e.g. 6-40cSt (l〇〇 ° C) the basic raw material, and shipped more easily form the product of W oligomerization process of the present invention is obtained. the product of the molecular weight range, typically 420W, 600W in most cases the viscosity and typically range 25-30cSt (10 (TC) oligomer extending to 2000. for the higher molecular weight and viscosity of the corresponding W be achieved by appropriate choice of reaction conditions. the polydispersity index (PDI) values ​​are typically 1.15 to 1.4, higher value associated with higher molecular weight oligomers within the range where no 同低聚物种类的数目随低聚程度增加而增加。该低聚中容易获得范围典型地超过90wt%的较高水平的产物转化率(二聚体到低聚物)。润滑剂馈分(C30+)通常为产物的85wt%或更高,典型地为90wt%。 Oligomer with the number of types increases with increasing degree of oligomerization. The oligomerization is typically readily available in a range of more than 90wt% conversion to product high level (dimer to oligomer) lubricant feed points ( C30 +) is typically the product of 85wt% or higher, typically 90wt%.

[0066] 本发明低聚工艺能实现的总反应方案可W如下所示,由初始a-締控进料出发,并通过用作本发明低聚步骤的进料的茂金属二聚体/ =聚体中间产物: [0066] The overall reaction scheme oligomerization process of the invention W may be achievable as follows, starting from the initial feed a- associated control, by acting as a feed and oligomerization step of the present invention, the metallocene dimer / = mer intermediate:

[00A71 [00A71

Figure CN105925340AD00101

[0068] 期望地,在用作润滑剂基本原料之前将源于路易斯酸催化步骤的润滑油范围低聚物产物氨化,由此除去任意残留不饱和度并由此稳定该产品。 [0068] Desirably, prior to use as a lubricant base stocks derived from the catalytic step lube range oligomer product of the Lewis acid amide, thereby removing any residual unsaturation and thereby stabilize the product. 氨化可WW对加氨处理传统PAO而言常见的方式来进行,使用例如金属(通常贵金属)氨化催化剂。 WW amination may be added to the ammonia treatment in terms of conventional PAO common way to carry out, for example, a metal (typically a noble metal) amide catalyst.

[0069] 下面实施例中,可W使用W02007011973、W02007011832或W02007011459中所述类型的合成方法来制备茂金属二聚体馈分。 [0069] In the following examples, W may be used W02007011973, W02007011832 or W02007011459 synthetic methods of the type metallocene dimer prepared feed points. 在实际采用的制备工序中,依据运些出版物中所述的方法纯化甲苯溶剂和进料O-締控,并在氮气气氛下进行所有合成步骤和操作,为了避免空气、氧、水分和其它毒物导致的任意催化剂失活或中毒。 In the actual preparation procedure adopted, the purification method of operation according to these publications and the toluene solvent feed O- association control, and all synthesis steps and operations under a nitrogen atmosphere, in order to avoid air, oxygen, water and other any catalyst poisons lead to deactivation or poisoning. 实施例 Example

[0070] 茂金属PAO可W利用如下示例性工序采用间歇模式操作来合成。 [0070] W can be a metallocene PAO using the following exemplary steps synthesized using a batch mode of operation. 将纯化的1-癸締(50g)和3.173gS异下基侣(TIBA)原料溶液在氮气气氛下注入500ml烧瓶中。 The association of the purified 1-decene (50g) and iso-yl 3.173gS Lu (of TIBA) was injected into the feedstock 500ml flask under nitrogen atmosphere. 随后在揽拌下将反应烧瓶加热到120°C。 Embrace then stirred at the reaction flask was heated to 120 ° C. 将安装于反应烧瓶之上的另一漏斗中含有20g甲苯、0.079g TIBA 原料溶液、0.430g rac-亚乙基双(4,5,6,7-四氨-1-巧基)二氯化错溶液和0.8012NCA原料溶液的溶液,在15分钟内加到1-癸締混合物中,同时保持反应溫度接近于120°C,上下不超过:TC。 The addition funnel is mounted on top of the reaction flask containing 20g of toluene, 0.079g TIBA raw material solution, 0.430g rac- ethylenebis (4,5,6,7-tetraamine -1- clever yl) dichloride 0.8012NCA error and a solution of a raw material solution, was added over 15 minutes 1-decene associative mixture while maintaining the reaction temperature close to 120 ° C, down no more than: TC. 使反应混合物在反应溫度下揽拌16小时。 The reaction mixture was stirred at embrace the reaction temperature for 16 hours. 随后关掉加热并将混合物用3ml异丙醇泽灭。 Then heat was turned off and the mixture was 3ml isopropanol Ze off. 随后将粗产物用100mL 5%化OH水溶液,随后用100mL去离子水洗涂S次。 The crude product was then 100mL 5% aqueous solution of OH, 100mL of deionized water followed by coating S times. 随后将有机层分离并用20g硫酸钢干燥1小时。 The organic layer was separated and then dried with 20g of steel sulfate for 1 hour. 滤出固体并将滤液首先通过低真空蒸馈进行蒸馈W除去甲苯、未反应的1-癸締和轻质締控二聚体馈分,随后通过高真空蒸馈在16(TC/1毫托真空下进行蒸馈W分离C30和更高的低聚物。随后可W将二聚体馈分与甲苯和未反应的单体通过蒸馈进行分离。 The solid was filtered off and the filtrate was evaporated firstly fed W toluene was removed, unreacted 1-decene dimer association and light control associated feed points by a low vacuum vapor feed, and then fed in 16 (TC / 1 mM distilled off by high vacuum W steaming feed separation C30 and higher oligomers subiculum vacuo. the dimers may then W feeding points with toluene and unreacted monomers were separated by evaporation feed.

[0071 ] 示例性实施例1:使用A1C13的轻质聚a締控的低聚 [0071] Exemplary embodiments Example 1: using a poly A lightweight A1C13 associated oligomerization control

[0072] 将通过上述一般工序制得的mPAO-二聚体(50.4g纯的)与0.4g水一起在氮气气氛下注入500ml圆底烧瓶中。 [0072] by the above general procedure prepared mPAO- dimer (50.4 g neat) into 500ml round-bottom flask under nitrogen atmosphere together with 0.4g water. 非常缓慢地加入无水AlCl3(2.5g) W保持溫度0-5°C。 Very slowly added anhydrous AlCl3 (2.5g) W maintaining the temperature at 0-5 ° C. 添加之后, 使反应在0-5°C下揽拌4小时,然后加入甲苯(100mL)。 After the addition, the reaction was stirred embrace at 0-5 ° C 4 hours, then added toluene (100mL). 使反应混合物升溫到室溫并随后继续揽拌16小时。 The reaction mixture was allowed to warm to room temperature and stirred for 16 hours then continues embrace. 通过添加25ml水使反应停止。 By adding 25ml of water to stop the reaction. 将产物用水(4X 50ml)和(IX 50ml)盐水洗涂,直到水层达到抑~7。 The product was washed with water (4X 50ml) and (IX 50ml) coating brine until the aqueous layer reaches 7 ~ suppression. 将有机层干燥并过滤。 The organic layer was dried and filtered. 随后通过旋转蒸发器除去低沸点(甲苯)组分,并通过使用Kugelrohr在160-170°C下真空下蒸馈除去高沸点组分(PAO-二聚体)。 Followed by removal of high-boiling components (dimers PAO-) remove low boiling (toluene) component, and evaporated under vacuum by using a Kugelrohr at 160-170 ° C by rotary evaporator feed. 将最终产物通过IR、GC、醒R和GPC进行表征。 The final product was characterized by IR, GC, R and wake GPC. GC分析显示为6.7 % PAO-二聚体、93.3 %润滑油产物。 GC analysis showed 6.7% PAO- as a dimer, 93.3% lube product. 发现蒸馈过的低聚物显示如表1中所示的性能: Found steamed oligomer feed through display performance as shown in Table 1:

[0073] 表1 「00741 [0073] Table 1 "00741

Figure CN105925340AD00111

LUU/t3」 不例性买砸例2:便用AiGi3的萊a筛危巧1-癸筛的巧化萊 LUU / t3 "does not buy cases of smashing Example 2: they use AiGi3 Lay a sieve risk Qiao Qiao sieve of 1-decyl Levin

[0076] 将如实施例1所用相同的mPAO-二聚体(40g纯的)与1-癸締(20g)和水(0.45g)-起在氮气气氛下注入500ml圆底烧瓶中。 [0076] The same as in Example 1 mPAO- dimer (40g neat) associated with the 1-decene (20g) and water (0.45 g of) embodiment - starting injection 500ml round bottom flask under nitrogen atmosphere. 非常缓慢地加入无水A1C13(3g) W保持溫度0-5°C。 Was added very slowly over anhydrous A1C13 (3g) W maintaining the temperature at 0-5 ° C. 添加之后,使反应混合物在〇-5°C下揽拌4小时,然后加入100mL甲苯。 After the addition, the reaction mixture was stirred at embrace billion-5 ° C 4 hours, then was added 100mL of toluene. 使反应混合物升溫到室溫并随后继续揽拌16小时。 The reaction mixture was allowed to warm to room temperature and stirred for 16 hours then continues embrace. 通过添加50ml水和75ml甲苯使反应停止。 By adding 75ml of toluene and 50ml of water to stop the reaction. 将产物用水(4 X 75ml) 和(lX750ml)盐水洗涂,直到水层达到抑~7。 The product was washed with water (4 X 75ml) and (lX750ml) coating brine until the aqueous layer reaches 7 ~ suppression. 将有机层干燥并过滤。 The organic layer was dried and filtered. 随后通过旋转蒸发器除去低沸点(甲苯)组分,并通过Kugelrohr在160-170°C下真空下除去高沸点组分(PAO-二聚体)。 It is then removed in vacuo by rotary evaporator to remove low-boiling (toluene) component, and by Kugelrohr at 160-170 ° C under high boiling components (PAO- dimer). 将最终低聚物产物通过IR、GC、醒R和GPC进行表征。 The final oligomer product, GC, and GPC R wake characterized by IR. GC分析显示产品转化率为95%, 6.31 %PA〇-二聚体和93.7%润滑油产物。 GC analysis showed 95%, 6.31% and 93.7% dimers PA〇- lube product conversion rate of products. 发现蒸馈过的低聚物显示如表2中所示的性能: Found steamed oligomer feed through display performance as shown in Table 2:

[0077] 表2 [0077] TABLE 2

Figure CN105925340AD00112
Figure CN105925340AD00121

L0079J 示例性实施例3-5:使用A1C13的PAO-二聚体与I-癸筛的共低聚 L0079J exemplary embodiment 3-5: use of A1C13 PAO- dimer dec screen co-oligomerization I-

[0080] 将无水AlCl3(2.7g)和12.Og癸烧在氮气气氛下注入500ml圆底烧瓶中。 [0080] Anhydrous AlCl3 (2.7g) and 12.Og burnt under nitrogen atmosphere dec injection 500ml round bottom flask. 非常缓慢地加入30.23g相同的纯mPAO-二聚体和15.16g 1-癸締(实施例3)的混合物,随后加入0.121g水和5g癸烧,并在低于40°C下强烈揽拌。 It was added very slowly 30.23g of pure mPAO- same decyl associated dimers and 15.16g 1- (Example 3) was added, followed by water and 5g 0.121g burn decyl, below 40 ° C and stirred strongly embrace . AlCb催化剂浓度等于2.5wt%。 AlCb catalyst concentration is equal to 2.5wt%. 添加水之后,使反应混合物在40°C下揽拌3小时,然后添加50ml水和150ml甲苯使反应停止。 After adding water, the reaction mixture was stirred embrace at 40 ° C 3 hours, and then added 150ml of toluene and 50ml of water to stop the reaction. 将产物用水(4 X 120ml)和(1 X 100mL)盐水洗涂,直到水层pH为~7。 The product was washed with water (4 X 120ml) and (1 X 100mL) coating brine, the aqueous layer until the pH was ~ 7. 随后将产物过滤并干燥。 The product was then filtered and dried. 通过Rotovap™除去低沸点(甲苯)组分,并通过真空下160~170°C下空气浴炉除去高沸点组分。 Remove low boiling (toluene) component, and the high-boiling components is removed under vacuum by 160 ~ 170 ° C air oven at a bath by Rotovap ™. 将最终产物通过GC和GPC进行分析。 The final product was analyzed by GC and GPC.

[0081] W相同方式在相同条件下进行实施例5和6,采用如下表3中所示不同摩尔比的mPAO二聚体/癸締。 [0081] W in the same manner for Examples 5 and 6 under the same conditions, using mPAO dimer / capric associate different molar ratios as shown in Table 3 below.

[0082] 表3中显示了蒸馈过的低聚物的分子量比(Mw,Mn)、产物转化率和润滑油产率,且表4中显示了它们的流变学性能。 [0082] Table 3 shows the feed vapor over the molecular weight oligomers ratio (Mw, Mn), product conversion and lube yields, and Table 4 shows the rheological properties thereof.

[0083] 示例性实施例6:使用A1C13的PAO-二聚体与1-癸締的低聚 [0083] The exemplary embodiment 6: Use of A1C13 PAO- associated dimer 1-decene oligomerization

[0084] 采用相同反应溫度、AlCb催化剂和催化剂浓度重复实施例3的工序,但是仅使用mPAO二聚体作为进料(无癸締),反应时间仅为0.5小时,由此制得更低分子量/更低粘度低聚物产物。 [0084] The same reaction temperature, AlCb catalyst and catalyst concentration step Example 3 was repeated, but using as the feed only mPAO dimer (dec no association), the reaction time was only 0.5 hours, whereby a lower molecular weight / lower viscosity oligomer product.

[0085] 表3中显示了蒸馈过的低聚物的分子量比(Mw,Mn)、产物转化率和润滑油产率,且表4中显示了流变学性能,证实了采用茂金属二聚体作为原材料制备低粘度(4-6cSt)产物的潜力。 [0085] Table 3 shows the feed vapor over the molecular weight oligomers ratio (Mw, Mn), product conversion and lube yields, and Table 4 shows the rheological properties, was confirmed using two metallocene mer starting material for preparing the low viscosity potential (4-6cSt) product.

[00化]表3 [0087] [Of 00] Table 3 [0087]

Figure CN105925340AD00122

[008引备注; [008 cited remarks;

[0089] 1.产物转化率:单体或进料转化为产物的数量或% [0089] 1. The conversion to product: the monomer feed is converted to the product or the number or%

[0090] 2.润滑油产物:通过GC测量的高于C30+的产物的数量 Higher than the amount measured by GC of C30 + product: [0090] 2. lube product

[0091] 表4 [0091] TABLE 4

[0092] 产物低聚物流变学 [0092] The oligomerization product stream rheology

[0093] [0093]

Figure CN105925340AD00123
Figure CN105925340AD00131

[0094]本文中引用的所有专利、试验工序、和其它文献,包括优先权文献,全部W与该公开内容相一致的程度引入作为参考且运种引入在容许的全部管辖权内。 All patents, test procedures [0094] herein by reference, and other documents cited, including priority documents, all W extent consistent with the disclosure of which is incorporated by reference and incorporated in all kinds of transport permissible jurisdiction.

[00M]虽然本文中公开的示例性形式已经特别地进行了描述,但是将理解,对于本领域技术人员而言各种其它改进形式是显而易见的且可W容易地实施,并不背离本公开内容的精神和范围。 [00M] While the illustrative forms disclosed herein have been particularly described, it will be appreciated that those skilled in the art that various other modifications will be apparent to and forms W can be easily implemented, without departing from the present disclosure the spirit and scope. 由此,所附权利要求的范围并非限定于本文中给出的实施例和描述,而是该权利要求应解释为包括本文中存在的可专利新颖性的所有特征,包括本发明所述属领域的技术人员将W其等价形式对待的所有特征。 Accordingly, the appended claims and not limited to the embodiments set forth herein described, but that the claims be construed to include all the features of patentable novelty exist herein, the present invention belongs to the field comprising W art which will treat all features of equivalents.

[0096]本文中列出数字下限和数字上限时,表示从任意下限到任意上限的范围。 [0096] numbers listed herein, lower and upper limit number that ranges from any lower limit to any upper limit.

Claims (10)

  1. 1. 低聚的聚α-烯烃的制备方法,包括在路易斯酸低聚催化剂的存在下使低分子量PAO 低聚物进行低聚,该低分子量PAO低聚物通过α-烯烃进料的茂金属催化低聚制得,其中该低分子量PAO低聚物包含α-烯烃进料的C 8H16~C3QH6()低聚物的混合物,其分子量范围为120~ 600、且末端烯烃含量为全部烯属不饱和度的至少25%。 A method for the preparation of oligomeric poly α- olefins comprising a low molecular weight PAO oligomer in the presence of a Lewis acid oligomerization catalyst oligomerization, metallocene low molecular weight PAO oligomer by olefin feed α- catalytic oligomerization prepared, wherein the low molecular weight PAO oligomer comprises C α- olefin feed is a mixture of oligomers 8H16 ~ C3QH6 (), having a molecular weight range of 120 to 600, and the terminal olefin content of all of the ethylenically unsaturated at least 25% saturation.
  2. 2. 权利要求1的方法,其中该低分子量PAO低聚物包含α-烯烃进料的C8H16~C3qH 6q低聚物的混合物。 The method of claim 1, wherein the low molecular weight PAO oligomer comprises a mixture of C8H16 ~ C3qH 6q oligomer α- olefin feed.
  3. 3. 权利要求1的方法,其中该低分子量PAO低聚物的末端烯烃含量为全部烯属不饱和度的至少50 %。 The method of claim 1, wherein the terminal olefin content of the low molecular weight PAO oligomer is at least 50% of all the olefinic unsaturation.
  4. 4. 权利要求1的方法,其中该α-烯烃进料包含(:8~&4进料。 The method of claim 1, wherein the olefin feed comprises α- (: ~ 8 & 4 feed.
  5. 5. 权利要求1的方法,其中该路易斯酸催化剂包括弗瑞德-克来福特催化剂。 The method of claim 1, wherein the Lewis acid catalyst comprises a Friedel - Crafts catalyst gram.
  6. 6. 权利要求5的方法,其中该弗瑞德-克来福特催化剂包括卤化铝或卤化硼。 The method of claim 5, wherein the Friedel - Crafts catalysts include gram aluminum halide or boron halide.
  7. 7. 权利要求6的方法,其中该卤化铝包括三氯化铝。 The method of claim 6, wherein the aluminum halide include aluminum trichloride.
  8. 8. 权利要求6的方法,其中该卤化硼包括三氟化硼。 The method of claim 6, wherein the boron halide comprising boron trifluoride.
  9. 9. 权利要求5的方法,其中该路易斯酸催化剂包括卤化铝或卤化硼与质子促进剂的组合。 9. The method of claim 5, wherein the Lewis acid catalyst comprises a combination of aluminum halide or boron halide with a proton accelerator.
  10. 10. 权利要求9的方法,其中该质子促进剂包括水。 10. The method of claim 9, wherein the protic promoter comprises water.
CN 201610267118 2008-03-18 2009-03-18 Process for synthetic lubricant production CN105925340A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US6982608 true 2008-03-18 2008-03-18
CN 200980109216 CN101977879A (en) 2008-03-18 2009-03-18 Process for synthetic lubricant production

Publications (1)

Publication Number Publication Date
CN105925340A true true CN105925340A (en) 2016-09-07

Family

ID=41089574

Family Applications (2)

Application Number Title Priority Date Filing Date
CN 201610267118 CN105925340A (en) 2008-03-18 2009-03-18 Process for synthetic lubricant production
CN 200980109216 CN101977879A (en) 2008-03-18 2009-03-18 Process for synthetic lubricant production

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN 200980109216 CN101977879A (en) 2008-03-18 2009-03-18 Process for synthetic lubricant production

Country Status (6)

Country Link
US (1) US8865959B2 (en)
EP (1) EP2265563A4 (en)
JP (1) JP5605715B2 (en)
CN (2) CN105925340A (en)
CA (1) CA2718879C (en)
WO (1) WO2009117110A3 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106867583A (en) * 2017-04-14 2017-06-20 上海欧勒奋生物科技有限公司 Method for efficiently preparing PAO50 basic oil
CN106957677A (en) * 2017-04-14 2017-07-18 上海欧勒奋生物科技有限公司 Method for synthesizing low-viscosity PAO4 by high-purity linear alpha olefine through anhydrous AlCl3

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007011459A1 (en) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Polyalpha-olefin compositions and processes to produce the same
WO2007011462A1 (en) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
US8299007B2 (en) 2006-06-06 2012-10-30 Exxonmobil Research And Engineering Company Base stock lubricant blends
US8921290B2 (en) 2006-06-06 2014-12-30 Exxonmobil Research And Engineering Company Gear oil compositions
US8501675B2 (en) 2006-06-06 2013-08-06 Exxonmobil Research And Engineering Company High viscosity novel base stock lubricant viscosity blends
US8834705B2 (en) 2006-06-06 2014-09-16 Exxonmobil Research And Engineering Company Gear oil compositions
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8394746B2 (en) 2008-08-22 2013-03-12 Exxonmobil Research And Engineering Company Low sulfur and low metal additive formulations for high performance industrial oils
US8247358B2 (en) 2008-10-03 2012-08-21 Exxonmobil Research And Engineering Company HVI-PAO bi-modal lubricant compositions
EP2351722A1 (en) * 2008-11-04 2011-08-03 Idemitsu Kosan Co., Ltd. Method for producing -olefin oligomer, -olefin oligomer, and lubricating oil composition
US8716201B2 (en) 2009-10-02 2014-05-06 Exxonmobil Research And Engineering Company Alkylated naphtylene base stock lubricant formulations
WO2011079042A3 (en) 2009-12-24 2011-09-09 Exxonmobil Chemical Patents Inc. Process for producing novel synthetic basestocks
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8748362B2 (en) 2010-02-01 2014-06-10 Exxonmobile Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
US8759267B2 (en) 2010-02-01 2014-06-24 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
WO2011125879A1 (en) * 2010-04-02 2011-10-13 出光興産株式会社 Lubricant composition for an internal combustion engine
US8703683B2 (en) * 2010-04-23 2014-04-22 Exxonmobil Research And Engineering Company Poly (alkyl epdxides), process for making, and lubricant compositions having same
US8524968B2 (en) * 2010-12-13 2013-09-03 Chevron U.S.A. Inc. Process to make base oil by oligomerizing low boiling olefins
US20140323665A1 (en) * 2011-03-30 2014-10-30 Exxonmobil Chemical Patents Inc. Polyalphaolefins by Oligomerization and Isomerization
CN103890151B (en) * 2011-10-10 2016-01-20 埃克森美孚化学专利公司 The method of poly-α- olefin composition and preparation of poly-α- olefin composition
US9422497B2 (en) 2012-09-21 2016-08-23 Exxonmobil Research And Engineering Company Synthetic lubricant basestocks and methods of preparation thereof
US9266793B2 (en) 2012-12-26 2016-02-23 Chevron Phillips Chemical Company Lp Acid-catalyzed olefin oligomerizations
US20140275664A1 (en) 2013-03-13 2014-09-18 Chevron Phillips Chemical Company Lp Processes for Preparing Low Viscosity Lubricants
ES2660464T3 (en) * 2013-06-28 2018-03-22 Dow Global Technologies Llc Process for preparing polyolefins branched lubricating applications
US9708549B2 (en) * 2013-12-18 2017-07-18 Chevron Phillips Chemical Company Lp Method for making polyalphaolefins using aluminum halide catalyzed oligomerization of olefins
US9732300B2 (en) 2015-07-23 2017-08-15 Chevron Phillipa Chemical Company LP Liquid propylene oligomers and methods of making same
EP3173462A1 (en) * 2015-11-30 2017-05-31 Fuchs Petrolub SE Transmission oil
US20170335217A1 (en) * 2016-05-19 2017-11-23 Chevron U.S.A. Inc. Alkylation of metallocene-oligomer with isoalkane to make heavy base oil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5498815A (en) * 1991-12-13 1996-03-12 Albemarle Corporation Preparation of synthetic oils from vinylidene olefins and alpha-olefins
CN1321169A (en) * 1999-09-23 2001-11-07 Bp阿莫科公司 Oligomer oils and their manufacture
EP1880986A1 (en) * 2005-05-12 2008-01-23 Idemitsu Kosan Co., Ltd. Process for producing saturated aliphatic hydrocarbon compound, and lubricant composition

Family Cites Families (131)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978442A (en) * 1957-05-01 1961-04-04 Du Pont Recovery process for polyethylene
NL135909C (en) * 1961-07-11
GB961903A (en) 1961-08-03 1964-06-24 Monsanto Chemicals Aliphatic hydrocarbons and their production
NL277638A (en) 1962-03-02
US3164578A (en) * 1962-07-26 1965-01-05 Du Pont Recovery process for polyolefins
US3382291A (en) * 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3780128A (en) 1971-11-03 1973-12-18 Ethyl Corp Synthetic lubricants by oligomerization and hydrogenation
US3742082A (en) * 1971-11-18 1973-06-26 Mobil Oil Corp Dimerization of olefins with boron trifluoride
US3769363A (en) * 1972-03-13 1973-10-30 Mobil Oil Corp Oligomerization of olefins with boron trifluoride
US3876720A (en) * 1972-07-24 1975-04-08 Gulf Research Development Co Internal olefin
US3883417A (en) * 1973-12-05 1975-05-13 Exxon Research Engineering Co Two-stage synthesis of lubricating oil
US4132663A (en) * 1975-03-17 1979-01-02 Gulf Research & Development Company Mineral oil compositions having improved pour point containing alpha-olefin copolymers
US4016349A (en) * 1975-10-30 1977-04-05 E. I. Du Pont De Nemours And Company Process for removing vanadium residues from polymer solutions
US4149178A (en) * 1976-10-05 1979-04-10 American Technology Corporation Pattern generating system and method
US4180575A (en) 1977-03-22 1979-12-25 Hoechst Aktiengesellschaft Triazolidino-pyridazine-diones
JPS5814408B2 (en) * 1977-08-31 1983-03-18 Lion Corp
JPS6041643B2 (en) * 1978-03-27 1985-09-18 Lion Corp
US4172855A (en) * 1978-04-10 1979-10-30 Ethyl Corporation Lubricant
US4263712A (en) * 1978-12-07 1981-04-28 Dale Products, Inc. Battery plate wrapping machine and method
US4239930A (en) * 1979-05-17 1980-12-16 Pearsall Chemical Company Continuous oligomerization process
US4263465A (en) * 1979-09-10 1981-04-21 Atlantic Richfield Company Synthetic lubricant
JPS56126315A (en) * 1980-03-11 1981-10-03 Sony Corp Oscillator
US4367352A (en) * 1980-12-22 1983-01-04 Texaco Inc. Oligomerized olefins for lubricant stock
US4956122A (en) * 1982-03-10 1990-09-11 Uniroyal Chemical Company, Inc. Lubricating composition
US4413156A (en) * 1982-04-26 1983-11-01 Texaco Inc. Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts
US4451684A (en) * 1982-07-27 1984-05-29 Chevron Research Company Co-oligomerization of olefins
US4469912A (en) * 1982-09-03 1984-09-04 National Distillers And Chemical Corporation Process for converting α-olefin dimers to higher more useful oligomers
US4587368A (en) * 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material
US4587374A (en) * 1984-03-26 1986-05-06 Ethyl Corporation Olefin isomerization process
CA1263498A (en) * 1985-03-26 1989-11-28 Mitsui Chemicals, Incorporated Liquid ethylene-type random copolymer, process for production thereof, and use thereof
US5177276A (en) * 1985-06-17 1993-01-05 Chevron Research Company Alpha-olefin oligomers useful as base stocks and viscosity index improvers, and lubricating oils containing same
US4701489A (en) * 1986-09-08 1987-10-20 El Paso Products Company Process for the production of stable noncorrosive amorphous polyalphaolefins
US4827064A (en) * 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
GB8701696D0 (en) 1987-01-27 1987-03-04 Exxon Chemical Patents Inc Crude & fuel oil compositions
CA1339142C (en) 1987-01-30 1997-07-29 Exxon Chemical Patents, Inc. Catalysts, method of preparing these catalysts and method of using said catalyst
DE3751694D1 (en) 1987-04-03 1996-03-14 Fina Technology Metallocene catalyst systems for the Polymersation of olefins, with a silicon hydrocarbyl bridge.
JP2524173B2 (en) * 1987-10-07 1996-08-14 出光石油化学株式会社 Olefin oligomer - method of manufacture
DE3743321A1 (en) 1987-12-21 1989-06-29 Hoechst Ag 1-olefinpolymerwachs and process for its manufacture
US4827073A (en) * 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
DE3808268A1 (en) * 1988-03-12 1989-09-21 Hoechst Ag A process for making a 1-olefin polymer
US5017714A (en) * 1988-03-21 1991-05-21 Exxon Chemical Patents Inc. Silicon-bridged transition metal compounds
JPH01292310A (en) * 1988-05-19 1989-11-24 Canon Inc Scanning optical device
US4912272A (en) * 1988-06-23 1990-03-27 Mobil Oil Corporation Lubricant blends having high viscosity indices
US4950822A (en) * 1988-06-27 1990-08-21 Ethyl Corporation Olefin oligomer synlube process
CA1321606C (en) 1988-06-27 1993-08-24 Matthew J. Lynch Olefin oligomer synlube process
US4892851A (en) * 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5186851A (en) * 1988-08-01 1993-02-16 Exxon Chemical Patents Inc. Ethylene alpha-olefin copolymer substituted mannich base lubricant dispersant additives
US5017299A (en) * 1988-08-01 1991-05-21 Exxon Chemical Patents, Inc. Novel ethylene alpha-olefin copolymer substituted Mannich base lubricant dispersant additives
US4910355A (en) * 1988-11-02 1990-03-20 Ethyl Corporation Olefin oligomer functional fluid using internal olefins
US4926004A (en) * 1988-12-09 1990-05-15 Mobil Oil Corporation Regeneration of reduced supported chromium oxide catalyst for alpha-olefin oligomerization
US4914254A (en) * 1988-12-12 1990-04-03 Mobil Oil Corporation Fixed bed process for high viscosity index lubricant
DE68902542D1 (en) 1989-01-03 1992-09-24 Mobil Oil Corp A process for producing the hydrogenated co-oligomeric.
DE3907965A1 (en) * 1989-03-11 1990-09-13 Hoechst Ag A process for producing a syndiotactic polyolefin
US4990709A (en) * 1989-04-28 1991-02-05 Mobil Oil Corporation C2-C5 olefin oligomerization by reduced chromium catalysis
US5012020A (en) * 1989-05-01 1991-04-30 Mobil Oil Corporation Novel VI enhancing compositions and Newtonian lube blends
EP0403866A1 (en) 1989-06-05 1990-12-27 MITSUI TOATSU CHEMICALS, Inc. Novel Poly-alfa-olefins
US4967032A (en) * 1989-09-05 1990-10-30 Mobil Oil Corporation Process for improving thermal stability of synthetic lubes
US5068487A (en) * 1990-07-19 1991-11-26 Ethyl Corporation Olefin oligomerization with BF3 alcohol alkoxylate co-catalysts
EP0513380B2 (en) 1990-11-30 2011-02-23 Idemitsu Kosan Company Limited Process for producing olefinic polymer
US5188724A (en) * 1991-02-06 1993-02-23 Pennzoil Products Company Olefin polymer pour point depressants
US5087788A (en) * 1991-03-04 1992-02-11 Ethyl Corporation Preparation of high purity vinylindene olefin
US5462995A (en) * 1991-06-11 1995-10-31 Nippon Zeon Co., Ltd. Hydrogenated products of thermoplastic norbornene polymers, their production, substrates for optical elements obtained by molding them, optical elements and lenses
US5688887A (en) * 1992-05-26 1997-11-18 Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US6043401A (en) * 1992-05-26 2000-03-28 Bp Amoco Corporation Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture
US5264642A (en) * 1992-06-19 1993-11-23 Mobil Oil Corp. Molecular weight control of olefin oligomers
GB9216014D0 (en) * 1992-07-28 1992-09-09 British Petroleum Co Plc Lubricating oils
US5220100A (en) * 1992-07-28 1993-06-15 Shell Oil Company Method of removing lithium compounds from a polymer
US5859159A (en) * 1992-12-17 1999-01-12 Exxon Chemical Patents Inc. Dilute process for the polymerization of non-ethylene α-olefin homopolymers and copolymers using metallocene catalyst systems
DE4304291A1 (en) * 1993-02-12 1994-08-18 Hoechst Ag Cycloolefin copolymers having a low melt viscosity and low optical attenuation
DE4304310A1 (en) * 1993-02-12 1994-08-18 Hoechst Ag Semi-crystalline cycloolefin copolymer film
EP0613873A3 (en) 1993-02-23 1995-02-01 Shell Int Research Oligomerisation process.
JPH06279320A (en) * 1993-03-26 1994-10-04 Idemitsu Petrochem Co Ltd Production of olefin oligomer
DE4415912A1 (en) 1994-05-05 1995-11-09 Linde Ag A process for the oligomerization of alpha-olefins to poly-alpha-olefins
US5612275A (en) * 1994-09-27 1997-03-18 Syracuse University Chemically active ceramic compositions with a phospho-acid moiety
WO1996023751A1 (en) 1995-02-01 1996-08-08 Basf Aktiengesellschaft Process for preparing olefin oligomers
DE69623528T2 (en) 1995-05-16 2003-03-20 Univation Tech Llc Production of polyethylene using a stereoisomeric metallocene
US5811379A (en) * 1996-06-17 1998-09-22 Exxon Chemical Patents Inc. Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267)
DE19645430A1 (en) * 1996-11-04 1998-05-07 Basf Ag Polyolefins and their functionalized derivatives
CN1234810A (en) 1997-07-22 1999-11-10 三井化学株式会社 Ethylene/alpha-olefin copolymer, compositions and process for preparation of copolymers and compositions
CA2306996A1 (en) 1997-10-16 1999-04-29 Teijin Limited Cyclic olefin polymer containing little catalyst residue, applications and production process thereof
WO1999055646A1 (en) * 1998-04-28 1999-11-04 Sasol Technology (Proprietary) Limited Production of dimers
DE19827323A1 (en) 1998-06-19 1999-12-23 Basf Ag Oligodecenes used as components of lubricants
US20030125495A1 (en) 1998-07-25 2003-07-03 Bp Chemicals Limited Alpha olefin-diene copolymers
US6180575B1 (en) * 1998-08-04 2001-01-30 Mobil Oil Corporation High performance lubricating oils
GB9816940D0 (en) * 1998-08-05 1998-09-30 Bp Chem Int Ltd Polymerisation catalysts
US6177527B1 (en) 1998-09-08 2001-01-23 Union Carbide Chemical & Plastics Technology Corporation Process for the preparation of polyethylene or polypropylene
US6087307A (en) * 1998-11-17 2000-07-11 Mobil Oil Corporation Polyether fluids miscible with non-polar hydrocarbon lubricants
US6147271A (en) * 1998-11-30 2000-11-14 Bp Amoco Corporation Oligomerization process
US6713438B1 (en) 1999-03-24 2004-03-30 Mobil Oil Corporation High performance engine oil
EP1083188A1 (en) * 1999-09-10 2001-03-14 Fina Research S.A. Catalyst and process for the preparation of syndiotactic / atactic block polyolefins
US6414091B2 (en) * 1999-12-15 2002-07-02 Sumitomo Chemical Company, Limited Thermoplastic resin, process for producing same and thermoplastic resin composition
JP4931269B2 (en) * 2000-05-30 2012-05-16 出光興産株式会社 Preparation and lubricant α- olefin polymer
US6858767B1 (en) 2000-08-11 2005-02-22 Uniroyal Chemical Company, Inc. Process for producing liquid polyalphaolefin polymer, metallocene catalyst therefor, the resulting polymer and lubricant containing same
DE60106937D1 (en) * 2000-08-18 2004-12-09 Univ Southampton holes with glass fibers, preforms and manufacturing processes
US6710007B2 (en) * 2001-01-26 2004-03-23 E. I. Du Pont De Nemours And Company Polymerization of olefinic compounds
WO2002066404A1 (en) * 2001-02-22 2002-08-29 Stichting Dutch Polymer Institute Catalyst system for the trimerisation of olefins
US6824671B2 (en) 2001-05-17 2004-11-30 Exxonmobil Chemical Patents Inc. Low noack volatility poly α-olefins
EP1410181A1 (en) 2001-07-16 2004-04-21 Yuqing Ren Embedded software update system
WO2003008459A9 (en) * 2001-07-20 2003-10-16 Univ Maryland Method for production of multimodal polyolefins of tunable composition, molecular weight, and polydispersity
CA2462169A1 (en) * 2001-08-31 2003-03-13 Shell Internationale Research Maatschappij B.V. Synthesis of poly-alpha olefin and use thereof
US6713582B2 (en) 2001-12-14 2004-03-30 Uniroyal Chemical Company, Inc. Process for the oligomerization of α-olefins having low unsaturation, the resulting polymers, and lubricants containing same
US6732017B2 (en) 2002-02-15 2004-05-04 Lam Research Corp. System and method for point of use delivery, control and mixing chemical and slurry for CMP/cleaning system
US6646174B2 (en) 2002-03-04 2003-11-11 Bp Corporation North America Inc. Co-oligomerization of 1-dodecene and 1-decene
US7351780B2 (en) * 2002-04-22 2008-04-01 Chevron Phillips Chemical Company, Lp Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts
US6706828B2 (en) * 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US6869917B2 (en) * 2002-08-16 2005-03-22 Exxonmobil Chemical Patents Inc. Functional fluid lubricant using low Noack volatility base stock fluids
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
WO2005108442A1 (en) 2002-10-15 2005-11-17 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US6960700B1 (en) 2002-12-19 2005-11-01 Uop Llc Adsorbent beds for removal of hydrides from hydrocarbons
JP2004277544A (en) 2003-03-14 2004-10-07 Tonen Chem Corp Method for producing modified polyolefin solution
CA2537311C (en) * 2003-09-13 2010-11-30 Exxonmobil Chemical Patents Inc. Lubricating compositions for automotive gears
US7473815B2 (en) * 2003-11-12 2009-01-06 Crompton Corporation Process for removal of catalyst residues from poly-α-olefins
JP2005200446A (en) 2004-01-13 2005-07-28 Mitsui Chemicals Inc α-OLEFIN (CO)POLYMER AND ITS USE
CN1938402B (en) * 2004-01-16 2010-12-01 合成石油公司 Process to produce synthetic fuels and lubricants
JP4714424B2 (en) * 2004-04-20 2011-06-29 Jx日鉱日石エネルギー株式会社 Method for producing α- olefin polymer
US8399390B2 (en) * 2005-06-29 2013-03-19 Exxonmobil Chemical Patents Inc. HVI-PAO in industrial lubricant and grease compositions
EP1743536B1 (en) * 2005-07-13 2016-10-19 Sympatex Technologies GmbH Method for producing waterproof stitched seams
WO2007011462A1 (en) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
US7989670B2 (en) 2005-07-19 2011-08-02 Exxonmobil Chemical Patents Inc. Process to produce high viscosity fluids
WO2007011459A1 (en) * 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Polyalpha-olefin compositions and processes to produce the same
CA2615895C (en) 2005-07-19 2012-10-30 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
US7601256B2 (en) * 2005-08-26 2009-10-13 Next-Ro, Inc. Reverse osmosis filtration systems
US7547811B2 (en) * 2006-03-24 2009-06-16 Exxonmobil Chemical Patents Inc. High viscosity polyalphaolefins based on 1-hexene, 1-dodecene and 1-tetradecene
US7592497B2 (en) * 2006-03-24 2009-09-22 Exxonmobil Chemical Patents Inc. Low viscosity polyalphapolefin based on 1-decene and 1-dodecene
US7544850B2 (en) * 2006-03-24 2009-06-09 Exxonmobil Chemical Patents Inc. Low viscosity PAO based on 1-tetradecene
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
WO2007145924A1 (en) 2006-06-06 2007-12-21 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst pao novel base stock lubricant blends
WO2008010862A1 (en) 2006-07-19 2008-01-24 Exxonmobil Chemical Patents Inc. Process to produce polyolefins using metallocene catalysts
US20100069687A1 (en) * 2006-09-06 2010-03-18 Chemtura Corporation Process for synthesis of polyalphaolefin and removal of residual catalyst components
US8513478B2 (en) 2007-08-01 2013-08-20 Exxonmobil Chemical Patents Inc. Process to produce polyalphaolefins
US7880047B2 (en) 2008-05-06 2011-02-01 Chemtura Corporation Polyalphaolefins and processes for forming polyalphaolefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5498815A (en) * 1991-12-13 1996-03-12 Albemarle Corporation Preparation of synthetic oils from vinylidene olefins and alpha-olefins
CN1321169A (en) * 1999-09-23 2001-11-07 Bp阿莫科公司 Oligomer oils and their manufacture
EP1880986A1 (en) * 2005-05-12 2008-01-23 Idemitsu Kosan Co., Ltd. Process for producing saturated aliphatic hydrocarbon compound, and lubricant composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106867583A (en) * 2017-04-14 2017-06-20 上海欧勒奋生物科技有限公司 Method for efficiently preparing PAO50 basic oil
CN106957677A (en) * 2017-04-14 2017-07-18 上海欧勒奋生物科技有限公司 Method for synthesizing low-viscosity PAO4 by high-purity linear alpha olefine through anhydrous AlCl3

Also Published As

Publication number Publication date Type
US20090240012A1 (en) 2009-09-24 application
CA2718879A1 (en) 2009-09-26 application
JP2011514381A (en) 2011-05-06 application
CN101977879A (en) 2011-02-16 application
WO2009117110A2 (en) 2009-09-24 application
US8865959B2 (en) 2014-10-21 grant
WO2009117110A3 (en) 2009-12-30 application
EP2265563A2 (en) 2010-12-29 application
CA2718879C (en) 2015-02-17 grant
JP5605715B2 (en) 2014-10-15 grant
EP2265563A4 (en) 2013-07-17 application

Similar Documents

Publication Publication Date Title
US5171908A (en) Synthetic polyolefin lubricant oil
US3763244A (en) Process for producing a c6-c16 normal alpha-olefin oligomer having a pour point below about- f.
US3780128A (en) Synthetic lubricants by oligomerization and hydrogenation
US7592497B2 (en) Low viscosity polyalphapolefin based on 1-decene and 1-dodecene
US4967032A (en) Process for improving thermal stability of synthetic lubes
US5113030A (en) High viscosity index lubricant compositions
US20030055184A1 (en) Synthesis of poly-alpha olefin and use thereof
US20100160506A1 (en) Production of synthetic hydrocarbon fluids, plasticizers and synthetic lubricant base stocks from renewable feedstocks
US20080177121A1 (en) Process to produce high viscosity fluids
US4263465A (en) Synthetic lubricant
US5136118A (en) High VI synthetic lubricants from cracked refined wax
US4962249A (en) High VI lubricants from lower alkene oligomers
US20090093657A1 (en) Process for preparing poly alpha olefins and lubricant basestocks from fischer-tropsch liquids
US6642169B2 (en) Polymerisation catalysts
US7544850B2 (en) Low viscosity PAO based on 1-tetradecene
US4906799A (en) Process for the production of reduced viscosity high VI hydrocarbon lubricant
US20100069687A1 (en) Process for synthesis of polyalphaolefin and removal of residual catalyst components
US20100317904A1 (en) Oligomerization of alpha olefins using metallocene-ssa catalyst systems and use of the resultant polyalphaolefins to prepare lubricant blends
US20090005279A1 (en) Polyalpha-Olefin Compositions and Processes to Produce the Same
US20090036725A1 (en) Process To Produce Polyalphaolefins
US4990713A (en) Process for the production of high VI lube base stocks
US20100323937A1 (en) Base stocks and lubricant blends containing poly-alpha olefins
WO2009137264A1 (en) Polyalphaolefins and processes for forming polyalphaolefins
US5026948A (en) Disproportionation of alpha-olefin dimer to liquid lubricant basestock
WO2009123800A1 (en) Production of shear-stable high viscosity pao

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination